Polymeric detergents comprising



Patented Nov. 23, 1948 UNITED stares POLYMERIC DETERGEN'IS COMPRISING WATER-SOLUBLE SALTS OF THE'HALF- ESTEBS OI" DICABBOXYLIC ACIDS AND THE FORMALDEHYDE CONDENSATES OFIIYDROCARBON-SUBSTITUTED PHE- NOXY-POLYALKOXY ALKANOLS Louis H. Bock, Huntingdon Valley, and James Bainey, Abington, Pa., assignor's to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 9, 1944, Serial No. 553,479

This invention relates to surface-active or capillary-active agents. It relates to the preparation of materials which have high detergent action under a wide variety of conditions. More specifically, it relates to the preparation and use of polymeric, water-soluble detergents which have high molecular weights and contain within each molecule a multiplicity of hydrophobic and hydrophilic groups or portions so arranged and balanced as to become oriented at an interface. '10

It is generally recognized that surface-active agents,- as,'for example, alkali-metal soaps or quaternary ammonium compounds, exist in water in the form of micelles. @While the exact nature of such miscelles is not established, there is evil5 dence that they are electrically charged aggregates of molecules. For example, when a sodium soap or a fatty acid is dispersed in water, it dissociates into positively charged sodium ions and into negative ions. Some of the latter apparently 20 based on measurements of freezing points, vapor pressures, and electrical conductivities of aqueous dispersions of surface-active agents. It is further recognized that surface activity is related to the formation of such micelles and to the orientation of the miscelles at an interface.

The individual molecules in colloidal micelles are held together only by physical forces or by weak secondary valences; and, as a result, the

extent of micelle formation depends upon theprevailing conditions, and it is afiected by such factors as the concentration of the surface-ac- ,tive agent, the presence of electrolytes, solvents, and other surface-active agents, and also upon the temperature. Thus, dilution of the solution, elevation" of the temperature,or a change in the amount of any salts which may also be present in solution'favor the reversion of micelles into simplemolecules and/or ions with the formation of true solutions. As an example, synthetic detergents known heretofore have no value at very low concentrationsor in very. hot water because under these conditions the micellar structure reverts, the molecules then exist in true solution, and, as a result, detergency isilost. The. neces sityof using relatively high concentrations plus 5 Claims. (01. 260-53) the higher cost of synthetic detergents combines to make the use of such detergents uneconomical and often impractical. Furthermore, the materials are ineffective in many laundering operations wherein extremely hot water is used in order toaccelerate the removal of soil.

The products of this invention difi'ere fromand have advantages over-detergents known heretofore in that their effectiveness is not. dependent upon the formation of loosely bound micelles. By the process of this invention, watersoluble macromolecules are synthesized in which all of the bonds between atoms are primary valence links and, hence, are strong and are not affected by such factors-as concentrationand temperature. Furthermore, the synthesized macromolecules contain balanced hydrophilie.

and hydrophobic groups so positioned in the macromolecule that orientation can and does occur readily at an interface.

The products of this invention may be made by condensing hydrocarbon-substituted phenols with formaldehyde to producepolymeric materials which are in fact macromolecules and then 25 introducing into said macromolecules hydrophilic groups. The hydrophilic groups, which impart water solubility, may be ether-alcohol groups or esterified ether-alcohol groups and are introduced, for example, by the reaction of ethylene oxide or a propylene oxide or va butylene oxide with the macromolecule. If desired, the terminal hydroxyl of said ether-alcohol group may be converted into a salt-forming ester groupof a polybasic acid.

The resultant products may be considered to have three functional portions. Thus, they contain (a) as the hydrophobic portion, the hydrocarbon groups attached to the phenol nucleus; (b) as the hydrophilic portion, the modified or unmodified ether-alcohol groups, and (c) as the polymeric portion, the ,phenol nuclei joined by i The hydrocarbon groups attached to the phenol and the modified or unmethylene bridges.

modified ether-alcohol groups also attached to the phenol are so balanced as to assure water solubility and orientation at an interface. At the same time, the polymeric nature of the product assures such a high molecular weightthat the product is in fact a macromolecule which imparts capillaryor surface-activity to a solution, as do micelles of ordinary soaps, but which is stable and is not dissociated as are the micelles of customary detergents under adverse conditions.

Theabove discussion is 'for purposes of the The polymeric detergentsof this invention have as their hydrophilic groups salt-forming carboxylic acid esters. The final products may be described as water-soluble, salt-forming "arboxylic esters of polymeric hydrocarbon-substituted phenoxy alcohols. They have the followin general formula:

but in every case must contain at least four carbon atoms. In reality, substituting groups of at least eight carbon atoms are much preferred.

Generally, it is preferred that the substituent hydrocarbon group be a, straight or branched chain'acyclic group, such as n-butyl, iso-butyl, tertiary butyl, amyl, tertiary amyl, n-octyl, diisobutyl, decyl, dodecyl, hexadecyl, octadecyl, and the like. Alternatively, phenols substituted with alicyclic groups may be used. These are typified by cyclohexyl .phenol, methyl-cyclohexyl phenol, butyl-cyclohexyl phenol, and dicyclohexyl phenol. While aryl-substituted phenols, such as p-phenyl phenol and p-naphthyl phenol, may be employed they are less satisfactory than those listed above unless they in turn contain an alkyl group. Thus, p-tolyl phenol is much preferred over p-phenyl phenol. Furthermore, a preference is given to the para-substituted phenols over those substituted in the ortho position. It is understood that although it is preferable to employ individual phenols, mixtures of phenols, for example, .p-tert.-

amyland p-diisobutyl-phenols, may be employed. The ratio of formaldehyde should be between 0.5 and 1.0 mol per mol of phenol. The formaldehyde may be used in the form of a solution, such as the formalin of commerce, or in a polymeric form such as' paraformaldehyde. Also, though not preferred, it may be in a form such as a formal or hexamethylene tetramine which will yield formaldehyde under the conditions of reaction.

Ordinarily, the substituted phenol and formaldehyde are reacted by condensing together in the presence of an acidic or alkaline condensation catalyst until the products have become relatively viscous. Solvents may be employed. Acidic condensation catalysts are preferred because of the ease with which the condensation may be controlled. Elevated temperatures naturally accelerate the rate of reaction. Condensation of formaldehyde and substituted phenols such as are here involved do not proceed to the infusible stage and, accordingly, no limit need be imposed upon the degree of condensation. In practice, it is convenient to follow the extent of condensation by means of viscosity measurements and the condensation may be halted at an early stage at which the molecular weight is low and the product on the average has no more than three or four phenolic units per molecule, or it may be continued until each macromolecule contains .many more units.

The condensation products may range in physical properties from ofls to brittle solids, depending upon the degree of condensation and the nature of the substituent hydrocarbon group on the phenol.

Polymeric detergents in which the hydrophilic or water-solubilizing groups are alcohols or saltforming esters thereof are the subjects of applications Serial Nos. 553,476, 553,477, and 553,478, filed of even date.

In this formula, R is a hydrocarbon substituent of at least four, and preferably over seven, carbon atoms; R is an alkylene group, preferably of two, three, or four carbon atoms, inclusive; R" is a hydrocarbon radical or group from the class consisting of alkyl and aryl radicals or groups containing preferably one to seven carbon atoms; 11 is an integer of a value of zero to twenty, inclusive, but preferably of a value between one and seven; M is one equivalent of a metal, preferably of an alkali metal such as sodium, potassium, or lithium or a group 11 metal such as beryllium,

- magnesium, calcium, barium, or strontium; z is an integer of a value equal to one or two, and a: is an integer greater than one.

These detergent products are preferably made by partially esterifying with an organic polycarboxylic acid a polymeric hydrocarbon-substituted phenoxy alcohol. The polymeric alcohols from which the esters are prepared may be made in various ways, as shown in detail in application Serial No. 553,476, filed of even date. Alkylene oxides, such as ethylene oxide, a propylene oxide, or a butylene oxide, may be condensed with a substituted phenol-formaldehyde macromolecule. The condensation is preferably conducted in the presence of an alkaline catalyst, such as a hydroxide of the alkali metals, although in some instances no catalyst is required. While this reaction may be carried out at lower temperatures and at atmospheric pressure in the presence of solvents, it is preferred to conduct it at temperatures above C. under superatmospheric pressure, also in the presence of solvents. One

,or more mols of the alkylene oxides may be reacted per mol of phenol condensed in the macromolecule. When one mol is' reacted, a simple alkylol group, R;OH, becomes attached, through the oxygen atom of the phenol, to the phenol nucleus of the macromolecule. Such com.- pounds have the general formula lil,

in which R is a hydrocarbon substituent of at In addition to 1 which is an integer, the-symbols Agitation was stopped and the contents of the in this formula have the same significance as flask were removed to a separatoryfunnel. The above. The'values of 11 which are preferred are aqueous and resinous layers were separated and one to six, although compounds in which 1 is the solvent was removed from the resinous layer as high as ten are shown to be valuable deter- .by vacuum distillation. After the removal of gents in the following examples and even those thesolvent, heating at a reduced pressure of 1.5

in which i/ is as h as twenty h ve merit to 2.5 mm. and at a temperature of 245 to 250 derivative of the phenol-formaldehyde conden- Alcohols typified by the above genera-1 fblmilas C. was continued for four and one-half hours.

m be made by another method- For example The condensate then had a viscosity of 4 0 poises halohydrms may be reacted with the sodium when measured as a 60% solution in toluene and,

sate. Typical halohydrins include the following: gggififigggg; 3 2 212 5 22 of the i product of step 1 was dissolved in 145.3 parts of CLCrH-i.O..CzHi.O.CzH .-OH toluene. (This corresponded to approximately,

nucsmocemon, and thelike. "Ihis reacone 1110!" Part of dilsobutylpheml) To this tion is also preferably conducted in the presence solution was added Parts of NaOH and of an alkaline catalyst, 133 parts (3.0 mols) of ethylene oxide, and the The alcohols described above may-be esterifled mixture was heated with stirring for one hour at with polycarboxylic acids or their equivalents b 120--136 C. in an autoclave. At the end of such as the anhydrides or acid halides. Suitable one hour, the pressure in th autoclave had p ly yli i s n l e ini iu a i dropped to twelve pounds per square inch at 136 adipic, phthalic, tricarballylic, hexahydrophthalic, C. ubstantially complete reaction citric, tartaric, and maleic. When esteriflcation of the ethylene oxide The product was a viscous takes Place between h alcohols the poly 25 solution having a solids content'of 76.1% and a carboxylic acids, there remain unreacted or free hydroxyl number of 118' acid groups which may then be neutralized to Step 3."-To the above solution was added 100 form salts. It is preferred to neutralize the partial esters of the acids with the hydroxides, parts of succmic acid anhydride' The mixture oxides, carbonates or bicarbonates 'of the group was refluxed for two hours which t I (alkali) metals or group II (especially alkaline Pmduct was disSOlved in 400 milliliters of a 10% earth) metals which produce water-soluble prod- Solution of NaOH- Toluene was removed by ucts. Obviously, salts. or the heavy metals can steam distinction- The uct. which had very be prepared in the same way. good detergent properties, had the formula:

I JO

; CaHi'l I sH i1 I The finalproducts, which are preferably watersoluble, are in' reality a combination of a salt 40 Example 2 and an ester and have the general formula given In Similar manner, e Product Of t p 2 of above. They may be described as surface-active Example 1 was esieriflcd with one moi of phihclic polymeric products of high molecular weight 3011-. anhydride and neutralized with one mol of sodium taming in their chemical structure salt-forming a n t n aqu us s luti n- Th produ t partial esters of organic poly'carboxylic acids and maintained its detergent properties both in Very hydrocarbon-substituted phenoxy alcohol units dilute solution and at h temperaturest had v in which the hydrocarbon substituent contains the formula:

CsHn J CsHi'i at least four carbon atoms, said phenoxyl alcohol Although the above examples are directed to units being joined by means of methylene bridges. the use of ethylene oxide, it is understood that a Following are examples of a preferred method propylene oxide or a butylene oxide may be emof preparing the products of this invention. ployed in a similar manner. As the length of the Example 1 hydrophilic group is increased. the product ordinariy becomes more water-soluble. It is, therep 1- ntc a thr e dflask equipped fore, advisable to increase the hydrophobic group with theremometer, mechanical agitator, and reproportionately. This can be done by increasing flux on nser was ch r d the f ll win 412 the size of the hydrocarbon substituent of the grams of diisobutyl phenol, 162 grams of a 37% phenol, asrepresented by R in the above genaqueous solution of formaldehyde, and 27.6 grams l f r l I thi ay, a balance is mainof water. The mixtur was a itated and heated tained between the hydrophilic and hydrophobic to a temperature of 90 C. At this point, 2.46 portions of the macromolecule so that the prodgrams of oxalic acid and 0.92 gram of Twitchells net is water-soluble and at the same time capllreagent 'dissolved in ten grams of water were lary-active. added. While being agitated, the reaction mix- All of the products of this invention function ture was refluxed for six hours; Two hundred as capillary-active or surface-active agents. As

grams of water and 384 grams of toluene were such, they become oriented at an interface, lower added, and refluxing was continued for an hour. the surface tension of water, and cause more 7 rapid wetting of surfaces such as the surfaces of fibers as measured by the standard Draves Sinking Test. Their outstanding property is their effectiveness as detergents. In this capacity, as

very high temperatures where former synthetic det rgents failed.

T ey are uncommonly advantageous in the laundering of cotton fabrics and in the securing of wool, sized, dyed, and printed fabrics in general. They may be used for preparing dispersions of oil in water or dispersions of polymerizable materials prior to the polymerization thereof.

2 atoms and wherein themodification of said con in which R'. is a saturated hydrocarbon sub-" stituent containing eight to eighteen carbon densation product consists of the group R0),,-R-oco-R"-coo1vi replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R in both occurrences is the same saturated alkylene group containing two to four carbon atoms, R" is a saturated hydrocarbon radical, containing one to seven carbon atoms, from the class consisting of alkylene and arylene radicals, 11 has a value of 0 to 20, and M is a metal from the class consisting of alkali and alkaline earth metals.

3. A modified phenol-formaldehyde condensation product having detergent properties wherein Also, they serve to break water-in-oll emulsions such as are encountered-in oil-fields. And they have been found to be very satisfactory in the treatment of leather, in the dispersion of pigments, and as assistants in dyeing.

The products of this invention are particularly useful when used in conjunction with other capilv-.lary-active agents, including fatty acid soaps and synthetic detergents such as those shown in United States Patents 2,115,192 and 2,143,759. Such combinations have extraordinarily high degrees of wetting and detergent properties.

We claim:

1. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mole of formaldehyde and one mole of a phenol from the class consisting of ortho-substituted and, para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substituent containing eight to eighteen carbon atoms and wherein the modification of said condensation product consists of the group (R0) yROCO-R" (COOM) 2 replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said I kaline earth metals, and 2 has a value of 1 to 2.

2. A modified phenol-formaldehyde condensation product having detergent properties wherein the'phenol-formaldehyde condensate is an .oily to brittle resinous condensation product of from 0.5 to 1.0 mole of formaldehyde and one mole of a phenol from the class consisting of ortho-substituted and para-substituted phenols, said phenol having the formula the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mole of formaldehyde and one mole of a phenol from the class consisting of orthosubstituted and para-substituted phenols, said phenol having the formula in which R is a saturated hydrocarbon substitu- I ent containing eight to eighteen carbon atoms and wherein the modification of said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereon wherein R" is a saturated hydrocarbon radical, containing one to seven carbon atoms, from'the class consisting of alkylene and arylene radicals, 11 has a value of 0 to 20, and 2 has a value of 1 to 2.

4. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to 1.0 mole of formaldehyde and one mole of an octyl phenol having the formula and wherein the modification of said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R" is a saturated hydrocarbon radical, containing one to seven carbon atoms, from the class consisting of alkylene and arylene radicals, 11 has a value of 0 to 20, and a has a value of 1 to 2.

'5. A modified phenol-formaldehyde condensation product having detergent properties wherein the phenol-formaldehyde condensate is an oily to brittle resinous condensation product of from 0.5 to-1.0 mole of formaldehyde and onemole of an octadecyl phenol having the formula and wherein the modification 01 said condensation product consists of the group replacing the original phenolic hydrogen atoms and being attached to each phenol nucleus in said condensate through the phenolic oxygen atom thereof, wherein R" is a saturated hydrocanbon radical, containing one to seven carbon atoms,

from the class consisting of alkylene and arylene 1 radicals, y has a value of 0 to 20, and 2 has a value of 1 to 2.

LOUIS H. BOCK. JAMES L. RAINE'Y.

REFERENCES CITED The following referencesare of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,917,250 Harris July 11, 1933 1,917,257 Harris July 11, 1933 2,046,318 Brubaker July 7, 1936 2,213,477 Steindorfl et a]. Sept. 3, 1940 FOREIGN PATENTS Number Country Date 576,177 Germany May 8, 1933 OTHER REFERENCES Clayton Theory of Emulsions, published "by Blakeston Co., Philadelphia, Pa., 4th ed. (1943). 

